Structure and properties of thiolatorhodium complexes, Rh(SC6H4-p-X)(PMe3)3 (X = Me, OMe)

Oxidative Addition of Water and Aliphatic Alcohols by IrCl(trialkylphosphine)3

“…This idea is best demonstrated in the oxidative addition of thiophenols to Rh(SAr)(PMe 3 ) 3 . Unlike all other examples cited, the type G product is more stable here due to steric reasons (thiophenolates are bulkier than PMe 3 ).…”

“…Based on it is D , our suggested structure for the transition state of reaction 3. We expect a similar transition state E for the rest of the oxidative additions of polarized bonds R−X mentioned above (R = H, alkyl; X = OH, O -alkyl, OC(O)CF 3 , halide, S -aryl). 11e,,,, The collapse of D and E to the final product should involve a concomitant weakening of the polarized bond and a rearrangement that enables coordination of X. Rearrangements within the equatorial plain have the lowest activation energies. 88a, Because X enters cis to R, the only possible products are F and G . Since the neutral ligand L 3 (L 2 in oxidative addition to cis- (CO)Ir(halide)(DPPE)) has a higher trans effect than the π-donor, the R group will enter trans to the π-donor, leading to type F products exclusively (Table ).…”

“…Stereochemical Course of the Reaction . Apart from reactions 2 and 3, there are only a few cases in which the identity of the kinetic product of polarized bond oxidative addition is known. 11e,,,, In all of them, irrelevant of the spatial arrangement of the different ligands, the polarized bond added across the axis containing the π-donor (the only exception being allyl-halides). σ-Donors or π-acceptors do not affect the stereochemistry in any of the examples we cite, in contrast to reports about hydrogen and silane oxidative additions. , We suggest that the stabilization imparted by the π -donating ligand to the transition state 21 accounts for this phenomenon.…”

“…Nevertheless, the type F compound was the kinetic product observed. It slowly isomerized to the type G compound …”

The Influence of Phosphane Coligands on the Nuclearity of Rhodium(I) 4-Thiolatobenzoic Acid Complexes

“…Stable mononuclear rhodium(I) complexes of the type [Rh(SR)(PR‘ 3 ) 3 ] with tertiary phosphane ligands are especially of interest, because they apparently show higher reactivity toward electrophiles than the well-investigated dinuclear thiolato-bridged complexes . To date, only a limited number of stable monomeric rhodium(I) thiolato complexes is known, that is, [Rh(SC 6 F 5 )(PR 3 ) 3 ] for PR 3 = PPh 3 , PMePh 2 , PMe 2 Ph, P(OMe) 3 , and P(OEt) 3 and [Rh(SR)(PMe 3 ) 3 ] for SR = SC 6 H 5 , 4-SC 6 H 4 Me, and 4-SC 6 H 4 OMe 5a, The tendency to dimerize decreases with decreasing electron density of the thiolato ligand and with increasing electron density of the phosphane ligands.…”